The controlled reversible addition-fragmentation chain transfer (RAFT) polymerization of ethoxyethylmethacrylate, isobornylmethacrylate, tert-butyl methacrylate and tert-butoxycarbonyloxystyrene has been studied. Is has been shown that only at tert-butoxycarbonyloxystyrene polymerization in the presence of benzyl dithiobenzoate a noticeable narrowing of the chain-length distribution (Mw/Mn = 1.19) is observed, which widens with the growth of conversion, as well as a linear growth of the number-average molecular weight with conversion. Other monomers have higher values of polydispersity (Mw/Mn = 1.6-2.0). The polymers isolated at the initial conversion give rise the secondary polymerization, i.e. they act as macroinitiators.